杂多酸绿色催化合成蒽醌反应的研究

Study on heteropoly acid green catalytic synthesis of anthraquinone

针对传统苯酐法合成蒽醌反应过程的严重环境污染问题,提出利用杂多酸绿色催化合成蒽醌的方法。以扩孔改性二氧化硅(SiO2)为载体,磷钨酸(HPW)为催化剂,制备负载型HPW/SiO2催化剂,系统考察其催化邻苯甲酰苯甲酸(BBA)合成蒽醌反应中不同性质溶剂的加入、溶剂用量、反应温度、反应时间、催化剂用量等对反应的影响,并对催化剂的重复使用性能进行了研究。实验结果表明,溶剂的加入对蒽醌收率具有较大影响,当选用环丁砜为溶剂,溶剂与BBA的质量比msolvent:mBBA=9,反应温度为200℃,反应时间为2 h,催化剂与BBA的质量比mcat:mBBA=1:1时,蒽醌收率可达91.12%。相比于无溶剂反应,催化剂具有更好的重复使用性能,4次重复使用后催化剂的活性仅下降了17.44%。

A green catalytic synthesis of anthraquinone(AQ)using heteropoly acid was proposed to solve the serious environmental pollution in the synthesis of anthraquinone by traditional phthalic anhydride method.The supported HPW/SiO2 catalysts were prepared using hole-expanded modified SiO2 as a carrier and phosphotungstic acid(HPW)as a catalyst,and used to catalyze the synthesis reaction of anthraquinone from o-benzoylbenzoic acid(BBA).The effects of different solvents,the amount of solvent,reaction temperature,reaction time,the amount of catalyst on the synthesis reaction of anthraquinone and the reuse performance of catalyst were systematically investigated.The experimental results indicate that the solvent has great influence on AQ yield,and that AQ yield could reach 91.12%under the optimal synthesis conditions:sulfolane as solvent,msolvent:mBBA=9,reaction temperature 200℃,reaction time 2 h,mcat/mBBA=1:1.Compared with the solvent-free reaction,the catalyst has better reusability performance,and the catalytic activity of the catalyst only decreases by 17.44%after 4 times of reuse.